Iodine Cuts Smog-Produced Ozone
Sun Offers Naphthalate As Polyester Component Dimethyl-2,6-naphthalate is result of study of acid-catalyzed dimethylnaphthalene isomerization 142ND
ACS
NATIONAL
MEETING
Organic Chemistry
Time (Hours)
Iodine May Be Smog Weapon Iodine added to irradiated or natural smog mixtures reduces ozone content 142ND
ACS NATIONAL
MEETING
Water and Waste Chemistry
By adding 10 parts per hundred million or less of iodine to test samples of irradiated or natural smog mixtures, the formation of ozone can be prevented or reduced substantially. According to Dr. William F. Hamilton, Myron Levine, and Eli Simon of Lockheed-California Co., Burbank, Calif., this could possibly provide an economical way of reducing smog. Partially burned or unburned hydrocarbons and oxides of nitrogen are the major pollutants responsible for smog. And the ratio of the concentrations of nitrogen oxides and hydrocarbon pollutants in the smog is important. For instance, diminishing the hydrocarbon concentration could lead to increased nitrogen oxide concentration, which then causes a reddish pall. The Lockheed-California scientists have shown the effects of iodine on a synthetic smog generated by a mixture of 100 p.p.h.m. pentene-1 and 100 p.p.h.m. of nitrogen dioxide in purified air in a 500-cu.-ft. Mylar-covered chamber. The direct addition of 6 p.p.h.m. of iodine to the irradiated 68
C&EN
SEPT. 24, 1962
samples caused a 7 5 % reduction in ozone concentration (62 to 15 p.p.h.m.) in less than an hour. If traces of iodine are present in a smog-forming mixture before irradiation, then excessive amounts of ozone don't form. Further experiments on other test samples show that in sunlight as well as in the dark, iodine reacts with ozone in purified air. The reaction ratio of ozone to iodine in both cases is about 4.5 to 1. This is in keeping with the suggested formation of iodous iodate by means of the over-all reaction: I 2 + 0 3 - » I ( I 0 3 ) 8 + 0 2 . The reaction is at least 10 times faster in sunlight than in the dark. The scientists believe that this is mainly the result of increased dissociation of the iodine molecule by photoenergy. Iodine is more effective in a photochemical smog atmosphere than in a purified air atmosphere—ozone to iodine ratios of only about 7 to 1 are needed. The scientists propose that this increased effectiveness of the iodine results from the quenching by the iodine of the free radical chain reactions that generate ozone. Dr. Hamilton and co-workers haven't as yet determined the toxicity of the reaction products, hence haven't made open air tests.
Sun Oil now has dimethyl-2,6naphthalate—the dimethyl ester of naphthalene-2,6-dicarboxylic acidavailable in developmental quantities. Currently selling at $5.00 per pound, the material is being offered by Sun as a possible successor, in part at least, to the widely used polyester component, dime thy Iter ephthala te. Preparation of dimethyl-2,6-naphthalate is the result of a basic research program that included a study of the acid-catalyzed isomerization of dimethylnaphthalene ( D M N ) isomers. The study was made by Dr. G. Suld and Dr. A. P. Stuart of Sun's basic research division. Sun has a heavy interest in naphthalene chemistry—its Toledo, Ohio, naphthalene plant has an annual capacity of more than 100 million pounds. Dimethylnaphthalenes are readily available from the mixed feedstocks for the naphthalene unit. Isomerization of dimethylnaphthalenes occurs in the presence of anhydrous hydrofluoric acid, promoted by boron trifluoride. Unique to DMN isomerization, compared to isomerization of xylenes (used to make dimethylterephthalate), is the appearance of three eauilibrium sets:
Another isomer, 1,2-DMN, is not in equilibrium with any other DMN isomer. The ratio of isomers present within a given set is affected by the amount of boron trifluoride added. The existence of such sets, Dr. Suld says, is probably due to the occurrence of energy barriers to the 1,2-methyl shift in the protonated DMN complexes. Even under the most favorable conditions, however, only about a third of total DMN isomers is convertible to
Now available in commercial quantities— the "Phenol with the Golden Arm"
GUAIACOL'S O R T H O - P O S I T I O N E D INERT M E T H O X Y G R O U P STEERS YOU TO U N I Q U E MOLECULAR LINKAGES These reactions suggest some of the interesting possibilities that guaiacol offers for development:
Guaiacol's methoxy radical in the ortho position m a t c h e s a molecular s t r u c t u r e that often occurs in nature . . . gives you a leg u p in building synthetics t h a t dupli cate or approximate natural products. Established applications for guaiacol in clude syntheses in t h e manufacture of per fumes, flavorings and drugs. Guaiacol has also been used as an "anti-skinning" agent for paints, and as a n antioxidant in petro leum specialties. I n making resins, t h e inert methoxy group blocks condensation out of one ortho posi tion. I t confines the polymer geometry to a limited build-up pattern; yields resins with lower molecular weights.
Return the coupon for literature that covers the reactions of guaiacol in greater detail. If you'd like to try out some reac tions on your own, write on your company letter head for samples.
Monsanto
Monsanto Chemical Company Organic Chemicals Division Dept. 259A, St. Louis 66, Missouri Please send me your Guaiacol Product Data File. Name Company Address City
Zone
State
C& Ε Ν
69
Chemical Characteristics
the 2,6-isomer. For this reason, the cost of dimethyl-2,6-naphthalate will probably always be greater than that of the terephthalate. Also, 2,6-DMN must be separated from a mixture of nine other isomers, whereas p-xylene, a major raw material in the production of dimethylterephthalate, need only be separated from three other isomers. Nevertheless, for certain uses the properties imparted to polyesters may override cost considerations, Dr. Suld points out. For example, the second order transition temperature of polyesters made with ethylene glycol and dimethyl-2,6-naphthalate is more than 100° C. And the polymers are unaffected by water. The second order transition temperature of the corresponding polyester from terephthalic acid is about 80° C. Thus, the naphthalene derivative can potentially be used to make truly washable fibers for textile fabrics that will neither lose nor develop creases during laundering in hot water. Sun has made developmental amounts of dimethyl-2,6-naphthalate available since the first of the year to makers of films and fibers. It has been used successfully in making polyamides as well as polyesters, according to Dr. Suld.
with Matching Size Eliminates Fertilizer Segregation
OXYALKYLATION Nalco toll or custom oxyalkylation may be the answer to special characteristics you are looking for in your non-ionics. Service is prompt, in any quantities you need—and Nalco chemists will gladly assist in getting the products you want. Write for details—tell us what you require.
NALCO CHEMICAL COMPANY 6199 West 66th Place
Chicago 38, Illinois
Subsidiaries in England, Italy, Mexico, Spain, Venezuela, and West Germany In Canada: Alchem Limited, Burlington, Ontario
, . Serving Industry through Practical Applied Science
70
C&EN
SEPT.
24,
1962
Segregation with dry blend fertilizers is result of particle size variation 142ND
ACS
NATIONAL
MEETING
Fertilizer and Soil Chemistry
Segregation—the major problem associated with dry blend fertilizers—is caused mostly by particle size variation of the ingredients. But close matching of the particle size distribution can just about eliminate the problem, since differences in shape and density of particles result in only minor variations in blended fertilizer compositions. These conclusions result from a study made by George Hoffmeister, Jr., S. C. Watkins, and Julius Silverberg, all of Tennessee Valley Authority. Economics favor bulk blending where possible (C&EN, Sept. 11,
1961, page 4 0 ) , and this could become the main form of fertilizer in the U.S. But, Mr. Hoffmeister points out, components of the mixture can segregate during handling and distribution. There are three handling operations generally considered as possible causes of segregation. One is the roHing action from coning, which occurs as storage piles are built, or as mixtures are transported, dumped, or bagged. The others are vibration and the ballistic action by fan spreaders attached to bulk trucks. Technologists have long suspected that the amount of segregation that might come from such handling depends on differences in size, shape, and density of the individual components of blends. But there has been little information on such variables. Before starting its study, TVA checked particle size distribution, apparent density, and particle shape of a number of commercial and TVA fertilizers available for use in dry blending. Most materials are within 6 to 16 mesh. However, there are variations within this range, Mr. Hoffmeister points out. Some materials are predominantly fine, between 10 and 16 mesh. Others have a predominating middle fraction, between 8 and 10 mesh. The apparent density measured by mercury displacement varies from 1.27 to 2.15 grams per milliliter. Particle shapes, rated visually, vary from well rounded granules to irregular fragments. Coning Studied. TVA's coning studies show that small differences in particle size cause serious segregation. Mixtures of two materials of irregular shape, but of unequal particle size, segregate as much as well rounded particles with similar size differences. Particles of equal size, but different shape, don't segregate. Differences in granule density cause only minor segregation. It isn't practical to use granules of only one size in a blend, however. So the investigators checked to see if they could maintain uniform composition by using ingredients with similar particle size distribution. This they did by forming 0-27-27 blends with matched and unmatched triple superphosphate and potash. With commercial granular materials, segregation caused composition in the pile to vary from 0-38-12 to 0-17-40. When the potash was screened to a Continued on page 74
Blockson Chemicals available for
Mixed Car Shipments DETERGENT PHOSPHATES Sodium Tripolyphosphate, Trisodium Phosphate, Tetrasodium Pyrophosphate, Polyphos® (Sodium Hexametaphosphate), Trisodium Phosphate Chlorinated, Tetrapotassium Pyrophosphate.
ADDITIONAL PHOSPHATES Disodium Phosphate, Monosodium Phosphate, Sodium Acid Pyrophosphate.
O T H E R B L O C K S O N CHEMICALS Teox® 12Ô Nonionic Surfactant, Teox® Compound 3, Sodium Fluoride, Sodium Silicofluoride, 70% Hydrofluoric Acid in drums. We are major producers of these chemicals. Write Olin district office for catalog or data.
ma
!
x3E
* o r m i x e d truck
Modern Detergents Mean Phosphates a n d Phosphates Mean Blockson
CHEMICALS DIVISION
lin
Olin Mathieson Chemical Corporation · New York · D I S T R I C T O F F I C E S : A t l a n t a · Buffalo · C h a r l o t t e Cinoinnati · H o u s t o n · Joliet · New Orleans · New York · Philadelphia · Providence · St. Louis · S a n Mateo C &Ε Ν
71
C&EN PROGRESS REPORT
INDUSTRIAL CHEMICAL SPECIALTIES
Companies added these products to their lines during the past four weeks Material
Company
Liquid soldering flux (Duzall) Modified epoxy resin coating (Nepoxide)
All-State Welding Alloys Co., Inc. White Plains, N.Y. Atlas Mineral Products Co. Mertztown, Pa.
Glass-filled nylon (Maranyl A 190) Epoxy cement (Chemgrip) Polystyrene (Styron 492)
Canadian Industries, Ltd. Toronto, Ontario Chemplast, Inc. East Newark, N.J. Dow Chemical Co. Midland, Mich.
Elastomeric sheet stock (Fairprene 20-050 FO) Radiation protection (NR1000)
Du Pont Fabric Division Wilmington, Del. Dyna-Therm Chemical Corp. Beverly Hills, Calif.
Extender plasticizer (Escoflex 125) Lacquer coating
East Coast Chemical Co. Cedar Grove, N.J. Excello Color Corp. Chicago, III.
Embedding agent (Durcupan ACM) Polyurethane plastic coating (U-2002)
Fluka, A. G., Chemische Fabrik Buchs, S. G., Switzerland Interplastic Corp. Commercial Resins Division St. Paul, Minn. Isomet Corp. Palisades Park, N J .
Large size lasers Cationic acrylic copolymer emulsions (Crilicon 274) Sperm whale myoglobin Contact adhesives Organic pigments Adhesives (R-84001, R-84002) Optically transparent glass (Ferroglass)
Jersey State Chemical Co. Haledon, N.J. Mann Research Laboratories, Inc. New York, N.Y. National Starch and Chemical Corp. New York, N.Y. Pylam Products Co., Inc. Queens Village, N.Y. Raybestos-Manhattan Bridgeport, Conn. Semi-Elements, Inc. Saxonburg, Pa.
Thermoplastic resins (phenoxy 8)
Stackpole Carbon Co. St. Mary's, Pa. Standard Chemical Products, Inc. Hoboken, N.J. Union Carbide Plastics Co. New York, N.Y.
Herbicide (Banvel D)
Velsicol Chemical Corp. Chicago, III.
Graphite and carbon Nonflammable coating
Available in commercial quantities unless otherwise noted.
72
C&EN
SEPT. 24, 1962
Features and
Uses
For use with all soft solders to bond precious and semiprecious metals Resistant to water solutions of nonoxidizing acids, alkalies, salts, and general corrosive conditions in petrochemical industry Replace metals in applications where coefficient of expansion is the same Bonds Teflon to all common materials Combines high heat resistance with low temperature properties and tough impact strength. Can be extruded or injection molded on conventional equipment Resistant to fuels and ozone. Can be used in packaging and gaskets Compounds of boron and lead dispersed in various epoxy, polyurethane, and silicone binders For use in formulating vinyl resin and rubber compounds For hard-to-print plastic surfaces in full range of opaque and transparent colors Hardens with practically no shrinkage when used with electron microscope For use as protective and decorative coating Calcium tungstate boules up to 4-, 5-, 6-, and 10-in. long depending on diameter For use in compounding industrial and household floor finishes First protein whose amino acid sequence has been determined by x-ray methods at a resolution of less than 2 A. Heat and water resistant, thermosetting, and contact adhesives can be applied by curtain coating techniques Offer brilliance, transparency, and fastness to light and solvents For use as sealing compounds for the ends of electronic wires and cables For use in thermomagnetic devices, microwave circulators, antennas, transformer coils, and other devices For use as electrode materials in fuel cells and special batteries For protecting spray booths and work areas from paint and adhesives Surface coating resins developed as maintenance coatings, metal primers, and wood finishes Approved experimental label permits limited use on wheat, barley, turf, and seed grasses
1133 laboratory instruments and appliances are made or you by Fisher Scientific's Manufacturing Division at Indiana, Pa. Here, exacting production standards guarantee satisfactory performance of every item. It's your assurance of the kind of quality that helps you do more and do it more accurately, more efficiently. Manufacturing—combined with product development, stocking and service—makes Fisher the single source that can supply whatever your laboratory needs. This eliminates any necessity for you to deal with several sources of supply. Full information about Fisher's service to science is in a new brochure, ' T h i s Is Fisher." For your copy, write Fisher Scientific Company, 101 Fisher Building, Pittsburgh 19, Pa. F-275 World's Largest Manufacturer-Distributor
of Laboratory Appliances & Reagent Chemicals
V\FÎ< F I S H E
R
S C Ι Ε Ν ΤΓ I F" I
ABSORBER
î!
C
size distribution similar to that of the triple superphosphate, composition ranged from 0-25-29 to 0-29-25. Al though the potash was specially screened, a commercial potash with roughly the same size distribution is available, Mr. Hoffmeister points out. This leads to some ground rules which should aid in reducing segre gation, Mr. Hoffmeister believes. For example, matching particle size distri bution should help. The materials should contain about equal percent ages of intermediate size fractions such as - 6 + 8, - 8 + 10, and - 1 0 + 16. Avoiding coning will also be an aid, especially where close size matching is not practical. Coning studies weren't accepted as the only test. Commercial, fan-type fertilizer spreaders distribute fertilizer through a ballistic throw. Again, results show that size differ ences can cause segregation, density is much less of a factor, and shape has no effect. Overlapping the passes of the spreader will reduce these effects, but might not be practical. Matching the particle size, however, should al most eliminate segregation due to bal listic action, Mr. Hoffmeister says.
Flame-Sprayed Polyethylene Coats Equipment and Surfaces
Impossible . . . no. Difficult. . . yes. Any problem looks that way before it's solved. That's where the challenge lies . . . and that's where Kay-Fries can help with a classical series of low molecular weight aliphatic polyf unctional molecules.* Technical literature, samples and advice are yours for the asking. KAY-FRIES
CHEMICALS,
INC. 360 Lexington Ave.,
N.Y.C,
*Barbiiuric Acid · Cyanoacetic Acid · Cyanoacefamide · Methyl and Ethyl Cyanoacetate · Λ4αlonic Acid · Diethyl Malonate · Dichloroacefic Acid · Methyl Dichloroacetate · Malonaldehyde Diacetal · Malononitrile · Methyl Chloroacetate · Methyl and Ethyl Orthoformate,
74
C&EN
SEPT.
2 4,
1962
Flame-sprayed polyethylene plastic coatings, used with new, improved primers, provide economical corrosion resistance for steel and other metallic surfaces, according to Schori Process Corp., Port Washington, L.I., N.Y. Powdered polyethylene coatings have been used increasingly in recent years to coat metals and other surfaces. For the most part, these dry powder coatings have been applied by rela tively slow techniques such as fluidized bed coating and dry powder dipping. Moreover, these techniques have been used mostly in finishing small metal products and are con sidered impractical for coating large metal surfaces such as tank walls and process equipment. Flame-spraying equipment, long used for applying other types of coat ings, has been adapted to handle specially formulated polyethylene powders. Improved copolymer prim ers available for use with this equip ment greatly increase the adhesion of flame-sprayed polyethylene to metals, wood, and concrete, Schori says. Since the copolymers are elastomeric,
they also permit workings of the liner when subjected to changing tempera tures, Schori adds. Schori, which specializes in flamespray coatings, says the technique gives a protective coating costing about one half that of earlier coatings and gives improved performance. The coatings are expected to find ex tensive use in maintenance of process ing equipment. Chemical storage tanks can be given corrosion protection by flame spraying. The powdered polyethylene coat ings can also be used to touch up un evenly dip-coated metal products. When applied to unheated metal sub strates, the flame-sprayed powdered polyethylene is said to provide a peelable coating useful in prototype pro duction or general corrosion protec tion. The polyethylene coating can be put on from virtually any angle with Schori's new Model Ρ flame spray unit. Metal surfaces are generally sand and grit blasted and preheated to about 400° F. Nonmetallic surfaces should be free from oil and moisture; some require no preheating while others must be heated to about 400° F. before coating. Schori mostly uses U.S. Industrial Chemicals' 100-mesh Microthene powdered polyethylene with its equip ment. The resin's good dispersion and batch-to-batch uniformity has been found to be an advantage, ac cording to Schori. Coatings ranging from 8 mils to l /2 in. thick can be applied with the Schori acetylene-air fired gun. Rates run to 20 lb. of powder per hour, covering up to 200 sq. ft. an hour with a 10-mil thick coating.
phase in the gas chromatography analysis of steroids, bile acids, and other high molecular weight com pounds. Excellent thermal stability and a high degree of polarity are claimed by the company. C2
Cobalt aluminate blue inorganic pig ment, Ferro V-3285, has been in troduced by the Color Division, Ferro Corp., Cleveland, Ohio. The pigment is the first in a new line of stronger inorganic pigments. It is suggested by the company for use in plastics and high temperature coatings. C 3
Chapter 18 Test quantities of a silica aerogel, Santocel 62, are now being offered paint manufacturers by the Inorganic Chemicals division of Monsanto Chemical Co., St. Louis, Mo. The material is said to be an improved flatting agent for lacquer, varnish, and other coatings. Commercial quantities are expected to be available next year, the company adds. C4
New concentrated butyl rubber latex has been introduced by Enjay Chemi cal Co., division of Humble Oil & Refining Co., New York, N.Y. Desig nated 90-91, the concentrated grade is a chemically stable emulsion of butyl rubber in water. It contains 6 1 % solids. It is said to be suitable for use in adhesives, roof coatings, paper saturation and coatings, nonwoven binders, textile dips and coat ings, emulsion paints, leather coat ings, and other applications. It is ideal for use in air barrier and food wrapping papers, Enjay claims. C 5
NEW CHEMICALS Developmental quantities of two aryl mercaptan derivatives are available from Pitt-Consol Chemical Co., Li brary, Pa. 2-Isopropylthiophenol and 4-bromothiophenol are suggested by the company for use in antioxidants, insecticides, pharmaceuticals, and resins. They can be used as resin modifiers and lube oil additives, the company adds. C1
New line of fluorosilicone rubbers has been developed by Vulcanized Rubber & Plastics Co., Morrisville, Pa. The materials range from moderate to ex ceptional resistance to fuel oil and solvent. The fluorosilicone compounds will not stick to mill rolls and will not crepe age, the company says. C6
Although Malonic Acid is probably best known for the reactions of its active methylene center, the utility of its carboxyl groups cannot be overlooked. Be cause most of us tihink of these groups simply as acid functions very little appears in the general literature concern ing their special value. The patent litera ture is quite a different story, however. Let's take a quick look at some recent patents now to see what ingenious chemists have been able to do with Malonic Acid. One group mills Malonic Acid into polyethylene to improve its adhesion to metal substrates and to improve the tensile strength of filled polyethylene, Another group makes a zinc salt catalyst which is highly effective for the prepara tion of vinyl esters by reaction of an acid with acetylene. They claim a substan tially longer service life from this catalyst as compared with their standard zinc acetate catalyst. Still another finds that use of Malonic Acid with calcium phytate provides a uniquely useful composition for reducing discoloration of cut vegetables and fruits. The patent presents quite a convincing story for such a product! And last, one of our favorites, is the potential use of the amine salts of Malonic Acid as germicides. Here are claimed preparations which might be incorporated into paints, plastics, adhesives, pharma ceuticals, etc. They show excellent activ ity against a wide spectrum of organisms such as S. aureus, S. pyrogenes, C. albicans, B. subtilis, P. ovale, the lactobacilli, etc, These are just some of the applications for Malonic Acid which appear in the newer patent literature. We will be glad to send you the patent numbers in case you are interested. Of course, it would be even better if you would like to try KayFries Malonic Acid to solve your own problems. Just write us in either case.
{
Cyanoethyl silicone rubber gum is of fered by Analytical Engineering Labo ratories, Inc., Hamden, Conn. The material can be used as a stationary
j |
Further useful information on keyed Chemical items mentioned is readily available . . .
I J
Use handy coupon on page 82
I
Kay-Fries Chemicals, Inc. 360 Lexington Ave., New York 17, Ν. Υ. SEPT.
2 4,
1α 62 C&EN
75
